The present invention relates to a sealant composition for a liquid crystal display cell, a production process for a liquid crystal display cell and a liquid crystal display element.
In recent years, a liquid crystal display panel (hereinafter referred to as a liquid crystal display element), having characteristics of a light weight and a thin size has come to be widely used as display panels for various devices including a personal computer. As liquid crystal display elements have come to be increasingly used, a use environment thereof has become more and more severe, and large-sized, homogeneous and high quality liquid crystal display cells have been desired.
A liquid crystal sealant composition means a thermosetting resin composition used for forming a cell prepared by charging liquid crystal between transparent glass substrates or transparent plastic substrates suitably provided with transparent electrodes and an alignment film which are important as members for constituting a liquid crystal display element and sealing it off so that it does not leak outsides.
Proposed are, for example, single liquid type thermosetting liquid crystal sealant compositions comprising an epoxy resin and a hydrazide base potential curing agent for epoxy resin and suitably containing a solvent. The above composition group satisfies sufficiently fundamental performances for sealing characteristics of a liquid crystal cell, that is, an adhesive sealing property, a heat resistance, an electric insulating property and a property of not staining liquid crystal, but bubbles through a seal (seal leak) have been liable to be generated in a single layer press hot bonding system which has been regarded as important as one of production systems for homogeneous and high quality liquid crystal display cells.
On the other hand, particularly a large-sized liquid crystal display has strongly been required in recent rears, and as a substrate used for a liquid crystal cell transfers to a large size, a liquid crystal sealant composition having high adhesion reliability which can meet such a large-sized substrate is required to be developed. At the same time, desired as well to be developed is a liquid crystal sealant composition which can meet a production system of a liquid crystal cell by a single layer press hot bonding system.
Further, the existing situation is that a liquid crystal sealant composition with which a high quality liquid crystal element capable of being used under further severer environment than ever, for.example, under a high humidity environment at 80xc2x0 C. can be produced has more and more strongly been required in recent years.
In order to produce a more homogeneous and higher quality liquid crystal display panel, a hot bonding step is actively tried to be improved in a production site of the above field. It has so far been recognized that, for example, a system in which many substrates are subjected to hot press bonding in a lump sum is good from a viewpoint of a productivity, and the system has widely been put to practical use. However, the system of the hot press bonding is a production system in which many sets of two substrates for constituting a liquid crystal cell having one substrate coated with a liquid crystal sealant composition are subject to cramping in vacuum in a piled-up state and then go through a hot bonding step in a heating furnace, and it has had the problem that the cells tend to make more or less a difference in a quality depending on upper, middle and lower positions in the pile.
Accordingly, the existing situation is that a single layer press hot bonding system, that is, a method in which a set of two transparent substrates for a liquid crystal cell is subjected set by set to hot press bonding for sealing has come to be proposed.
In the above single layer press hot bonding system, however, a publicly known liquid crystal sealant composition of a single liquid hot curing type has been liable to bring about problems such as generation of bubbles through a seal (seal leak), a marked disturbance in a seal width and an increase in stain in the vicinity of a sealed part (generation of inferior liquid crystal display).
Accordingly, the existing situation is that strongly required is a novel liquid crystal sealant composition which can meet the single layer press hot bonding system and exhibit high productivity and which is durable under a high humidity environment of 80xc2x0 C.
Under such social background as described above, a subject to be solved is to provide a liquid-crystal sealant composition which can meet a substrate for a large-sized liquid crystal element and exhibit high productivity in the single layer press hot bonding system and which can provide a liquid crystal element durable over a long period of time even under a high humidity environment of 80xc2x0 C., more specifically to provide a liquid crystal sealant composition which is highly fitted to single layer press and in which a liquid crystal display cell obtained using the composition is excellent in a heat resistance and a moisture barrier property and can secure dimensional stability and long-time display stability.
Further, another subject is to provide a production process for a liquid crystal cell using the above liquid crystal sealant composition.
Intensive investigations repeated by the present inventors in order to solve the subjects described above have resulted in finding that the subjects described above can be achieved by a composition comprising a specific epoxy resin, a specific potential curing agent for epoxy resin, a specific rubber-like polymer fine particle, a specific inorganic filler, a specific high softening point-polymer fine particle, and if necessary, a silane coupling agent, a curing accelerator, a solvent and a gap-forming controller each falling in a specific range, and thus the present invention has been completed.
That is, the liquid crystal sealant composition of the present invention comprises the following items [1] to [11]:
[1] A liquid crystal sealant-composition comprising an epoxy resin composition, wherein
(a) an aqueous solution obtained by admixing the above composition with the same mass of purified water has an ionic conductivity of 1 mS/m or less and
(b) a coated material obtained by coating the above epoxy resin composition in a thickness of 50 xcexcm and subjecting it to heat treatment at 80 to 100xc2x0 C. for 20 minutes has a viscosity of 50 to 10000 Paxc2x7s at 80 to 100xc2x0 C. by an E type viscometer; and in a cured matter of the above epoxy resin composition,
(c) the cured matter of the above composition has a linear expansion coefficient of 10xc3x9710xe2x88x925 mm/mm/xc2x0 C. or less at 0xc2x0 C. to 100xc2x0 C., which is determined by means of a thermomechanical analyzer (TMA),
(d) the cured matter of the above composition has a glass transition temperature Tg of 100xc2x0 C. or higher, which is deteried by means of a thermomechanical analyzer (TMA), and
(e) a cured matter having a thickness of 100 xcexcm which is formed from the above composition has a moisture permeability of 200 g/m2xc2x724 hours or less at 80xc2x0 C. at which moisture passes through the above cured matter.
[2] The liquid crystal sealant composition as described in the above item [1], comprising:
20 to 88.9 mass % of an epoxy resin (1) having 1.2 or more epoxy groups on an.average in a molecule,
1 to 15 mass % of a rubber-like polymer fine particle (2) having a softening point of 0xc2x0 C. or lower and a primary particle diameter of 5 xcexcm or less,
5 to 50 mass % of an inorganic filler (3),
5 to 30 mass.% of a thermally active potential curing agent for epoxy resin (4), and
0.1 to 9.5 mass % of a high softening point-polymer fine particle (5) having a softening point of 50xc2x0 C. or higher and a primary particle diameter of 2 xcexcm or less.
[3] The liquid crystal sealant composition as described in the above item [2], further comprising 0.1 to 5 mass % of a silane coupling agent (6) and 0.1 to 10 mass % of a curing accelerator (7).
[4] The liquid crystal sealant composition as described in the above item [2] or [3], further comprising 1 to 25 mass % of a solvent (8) which is compatible with the epoxy resin and has a boiling point falling in a range of 150 to 230xc2x0 C.
[5] The liquid crystal sealant composition as described in any of the above items [2] to [4], further comprising 0.1 to 5 mass % of a gap-forming controller (9).
[6] The liquid crystal sealant composition as described in any of the above items [2] to [5], wherein a maximum exothermic peak temperature determined from a thermogram obtained by differential scanning calorimetry (DSC) in which 10 mg of the composition described above is heated at a constant rate of 5xc2x0 C./minute in an inert gas atmosphere falls in a range of 135 to 180xc2x0 C.
[7] The liquid crystal sealant composition as described in any of the above items [2] to [6], wherein the composition described above is a single-liquid type epoxy resin composition, and an exothermic initiation temperature determined from a thermogram obtained by differential scanning calorimetry (DSC) in which 10 mg of the liquid crystal sealant composition is heated at a constant rate of 5xc2x0 C./minute in an inert gas atmosphere falls in a range of 60 to 130xc2x0 C.
[8] The liquid crystal sealant composition described in any of the above items [4] to [7], wherein the epoxy resin (1) described above is an epoxy resin having 1.7 or more epoxy groups on an average in a molecule and has a polystyrene-reduced number average molecular weight of 7000 or less which is determined by gel permeation chromatography measurement.
[9] The liquid crystal sealant composition as described in any of the above items [4] to [8], wherein the rubber-like polymer fine particle (2) and the high softening point-polymer fine particle (5) described above are present in the state that they are dispersed in the epoxy resin in the form of particles respectively.
[10] The liquid crystal sealant composition as described in any of the above items [4] to [9], wherein the high softening point-polymer fine particle (5) is a high softening point-polymer fine particle which comprises a poly(meth)acrylate having a micro cross-linking.structure as a main component and has a softening point of 60 to 150xc2x0 C. and a primary particle diameter falling in a range of 0.01 to 5 xcexcm and which contains an epoxy group introduced into a polymer component in a proportion of 0.1 to 5 mass %.
[11] The liquid crystal sealant composition as described in any of the above items [4] to [10], wherein at least a part of the inorganic filler (3) is graft-bonded with 1 to 50 mass parts of the epoxy resin or the silane coupling agent per 100, mass parts of the inorganic filler in terms of a grafting rate represented by a mass increasing rate determined by a repetitive solvent-washing method.
[12] The liquid crystal sealant composition as described in any of the above items [4] to [11], wherein the solvent (8) described above is at least one selected from a ketone solvent, an ether solvent and an ester solvent each having a boiling point falling in a range of 150 to 230xc2x0 C.
[13] A production process for a liquid crystal display cell, comprising:
printing or dispenser-coating the liquid crystal sealant composition as described in any of the above items [1] to [12] on a bonding-sealing part of a glass-made or plastic-made substrate for a liquid crystal cell and precuring it at 70 to 120xc2x0 C.,
then adjusting the position in a pair with a substrate which is not subjected to the treatment described above,
subjecting the paired substrates to hot press treatment at 100 to 200xc2x0 C. to bond and fix in a homogeneous thickness falling in a range of 3 to 7 xcexcm to form a cell, and
then charging a liquid crystal material into the above cell and sealing the injection port with a two-liquid type liquid crystal sealant composition.
[14] A liquid crystal display element obtained by:
printing or dispenser-coating the liquid crystal sealant composition as described in any of the above items [1] to [12] on a bonding-sealing part of a glass-made or plastic-made substrate for a liquid crystal cell and precuring it at 70 to 120xc2x0 C.,
then adjusting the position in a pair with a substrate which is not subjected to the treatment described above,
subjecting the paired substrates to hot press treatment at 100 to 200xc2x0 C. to bond and fix in a homogeneous thickness falling in a range of 3 to 7 xcexcm to obtain a cell, and
then charging a liquid crystal material into the above cell and sealing the injection port with a two-liquid type liquid crystal sealant composition.
The liquid crystal sealant composition of the present invention is a composition, wherein:
(a) an aqueous solution obtained by admixing the above composition with the same mass of purified water has an ionic conductivity of 1 mS/m or less and
(b) a coated material obtained by coating the above epoxy resin composition in a thickness of 50 xcexcm and subjecting it to heat treatment at 80 to 100xc2x0 C. for 20 minutes has an a viscosity of 50 to 10000 Paxc2x7s at 80 to 100xc2x0 C. by an E type viscometer; and in a cured matter of the above epoxy resin composition,
(c) the cured matter of the above composition has a linear expansion coefficient of 10xc3x9710xe2x88x925 mm/mm/xc2x0 C. or less at 0 to 100xc2x0 C., which is determined by means of a thermomechanical analyzer (TMA),
(d) the cured matter of the above composition has a glass transition temperature Tg of 100xc2x0 C. or higher, which is determined by means of a thermomechanical analyzer (TMA), and
(e) the cured matter of the above composition having a thickness of 100 xcexcm has moisture permeability of 200 g/m2xc2x724 hours or less at 80xc2x0 C. at which moisture passes through the above cured matter.
The condition of (b) is, for example, a physical property required for a sealing material in a hot bonding step in producing a large-sized liquid-crystal display, to be more specific, in a B stage. A viscosity of this B stage-reduced composition by an E type viscometer is controlled to 50 Paxc2x7s or more at 80 to 100xc2x0 C., whereby seal leak is notably inhibited from being generated, for example, at the time of single layer press hot press bonding (hereinafter referred to merely as single layer press or single layer hot press), and they are substantially prevented from being generated. Also, the viscosity is controlled to 10000 Paxc2x7s or less at 80 to 100xc2x0 C., whereby it becomes easy to control the desired gap width, for example, at the time of single layer press hot press bonding, and the work efficiency is raised. Accordingly, it is preferred.
Further, the composition obtained after the heat treatment described above has a viscosity falling more preferably in a range of 75 to 5000 Paxc2x7s at 80 to 100xc2x0 C. by an E type viscometer, particularly preferably 100 to 1000 Paxc2x7s.
The liquid crystal sealant composition of the present invention has a maximum exothermic peak temperature falling preferably in a range of 135 to 180xc2x0 C., which is determined from a thermogram obtained by differential scanning calorimetry (DSC) in which 10 mg of the liquid crystal sealant composition of the present invention is heated at a constant rate of 5xc2x0 C./minute in an inert gas environment. The peak temperature controlled to 135xc2x0 C. or higher can secure the quick curing property at a low temperature at the time of single layer hot press bonding. On the other hand, the peak temperature controlled to 180xc2x0 C. or lower can avoid the production conditions of a liquid crystal cell from becoming severer than needed.
When the liquid crystal sealant composition of the present invention is a single-liquid type epoxy resin composition, the exothermic initiation temperature determined from a thermogram obtained by differential scanning calorimetry (DSC) in which 10 mg of the liquid crystal sealant composition is heated at a constant rate of 5xc2x0 C./minute in an inert gas environment falls preferably in a range of 60 to 130xc2x0 C. The initiation temperature controlled to 60xc2x0 C. or higher can secure the viscosity stability in handling the liquid crystal sealant composition in the vicinity of room temperature. On the other hand, the initiation temperature controlled to 130xc2x0 C. or lower can secure the quick curing property at a low temperature at the time of single layer hot press bonding.
A moisture permeability of the cured matter of the liquid crystal sealant composition at 80xc2x0 C. is controlled to a specific range, whereby durability of liquid crystal can notably be elevated. That is, the moisture permeability at 80xc2x0 C. represented by a permeating amount of moisture passing through the cured film of the liquid crystal sealant composition having a thickness of 100 xcexcm for 24 hours under an environment of 80xc2x0 C. and 95% relative humidity is controlled to 200 g/m2xc2x724 hours or less, whereby moisture can notably be inhibited from penetrating into the liquid crystal display cell for short time, which results in preventing uneven display and a reduction in response speed. Stable operation even under a high temperature and a high humidity, which is particularly required in recent years, can be maintained over a long period of time.
In the liquid crystal sealant composition of the present invention, the moisture permeability at 80xc2x0 C. is controlled more preferably to less than 150 g/m2xc2x724 hours, particularly preferably less than 100 g/m2xc2x724 hours.
Further, the glass transition temperature characteristic (Tg characteristic) of the cured matter of the liquid crystal sealant composition is controlled to a specific range, whereby a range of the usable area of liquid crystal can be expanded. In particular, it becomes possible to use it under a higher temperature than required in recent years. That is, the glass transition temperature (Tg) of the cured matter, which is determined by means of a thermomechanical analyzer (TMA) is controlled to 100xc2x0 C. or higher, whereby it becomes possible to use the resulting liquid crystal display element at a higher display reliability temperature for long time. To be more specific, the reliability can be secured when the resulting liquid crystal display element is exposed for long time under a high temperature environment of 80xc2x0 C. The glass transition temperature is more preferably 110xc2x0 C. or higher and falls particularly preferably in a range of 115 to 180xc2x0 C.
Further, the linear expansion coefficient of the cured matter of the liquid crystal sealant composition at 0 to 100xc2x0 C. is controlled to a specific range, whereby the dimensional stability of the resulting liquid crystal display element can be secured. The linear expansion coefficient of the cured matter of the liquid crystal sealant composition is controlled to 10xc3x9710xe2x88x925 mm/mm/xc2x0 C. or less, whereby disordered display and a reduction in the response speed can be prevented for long time even under a high temperature and a high humidity.
In the liquid crystal sealant composition of the present invention, the linear expansion coefficient of the cured matter which is determined by means of a thermomechanical analyzer (hereinafter referred to merely as TMA) is controlled preferably to less than 5xc3x9710xe2x88x925 mm/mm/xc2x0 C., particularly preferably less than 3xc3x9710xe2x88x925 mm/mm/xc2x0 C.
In the liquid crystal sealant composition of the present invention, a barometer of a free ion concentration in the liquid crystal sealant composition is an ionic conductivity of an aqueous solution prepared by admixing the liquid crystal sealant composition with the same mass of purified water for 5 to 30 minutes, and the ionic conductivity thereof is controlled to 1 ms/m or less. The long-term display functionality of the finally resulting liquid crystal display element can be maintained by controlling the ionic conductivity thereof to 1 ms/m or less. It is controlled preferably to 0.5 mS/m or less, particularly preferably 0.2 mS/m or less.
The liquid crystal sealant composition of the present invention comprises an epoxy resin (1) having 1.2 or more epoxy groups on an average in a molecule [hereinafter referred to merely as the epoxy resin (1)], a rubber-like polymer fine particle (2) having a softening point of 0xc2x0 C. or lower and a primary particle diameter of 5 xcexcm or less, an inorganic filler (3), a thermally active potential curing agent for epoxy resin (4) [hereinafter referred to merely as the curing agent (4)], a high softening point-polymer fine particle (5) having a softening point of 50xc2x0 C. or higher and a primary particle diameter of 2 xcexcm, and if necessary, a silane coupling agent (6), a curing accelerator (7), a solvent (8) which is compatible with the epoxy resin and inactive to an epoxy group [hereinafter referred to merely as the solvent (8)], a gap-forming agent (9) and other additives.
Next, the structural components shall specifically be explained.
The epoxy resin (1) used in the present invention is an epoxy resin having 1.2 or more epoxy groups on an average in a molecule. It has preferably 1.7 or more epoxy groups, particularly preferably 2 to 6 epoxy groups on an average in a molecule. The epoxy group is controlled to 1.2 or more groups on an average in a molecule, whereby the heat resistance is improved. The epoxy resin may be a single resin or a mixture of different resins, and the resins which are either solid or liquid at room temperature can be used.
The epoxy resins used in the present invention shall not specifically be restricted as long as they are epoxy resins having the prescribed epoxy groups or a mixture thereof, and mixture of monofunctional epoxy resins and multifunctional epoxy resins or the multifunctional epoxy resins alone or a mixture thereof can be used. Further, modified epoxy resins thereof can preferably be used as well. Though not specifically be restricted, the number of functional groups per a molecule of the epoxy resin contained in the liquid crystal sealant composition can be determined by the epoxy group equivalent and the mass average molecular weight which is obtained by fractionating by means of a liquid chromatography.
The particularly preferred epoxy resin (1) has an ionic conductivity of preferably 2 mS/m or less, more preferably 1 mS/m or less and particularly preferably 0.5 mS/m or less in terms of an ionic conductivity of extract water which is obtained by contacting and mixing the single resin or the mixture of a plurality thereof with the same mass of purified water for 30 minutes.
If the above extract water has an ionic conductivity of 2 mS/m or less, a free ion can notably be inhibited or substantially avoided from transferring to the liquid crystal phase in bringing liquid crystal into contact with the cured matter of the finally obtained liquid crystal sealant composition of the present invention. When two or more different kinds of the epoxy reins are used, the total content of the free ions contained in the mixture thereof better satisfies the requisite described above.
The epoxy resin (1) is preferably a mixture of an epoxy resin (1-1) which is liquid in a temperature range of 0 to 50xc2x0 C. and an epoxy resin (1-2) which is solid in a temperature range of 0 to 50xc2x0 C. Also, the above mixture preferably becomes liquid at 0 to 120xc2x0 C.
The epoxy resin (1-2) which is solid in a temperature range of 0 to 50xc2x0 C. in the mixture is preferably at least one resin selected from a cresol novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a triphenolmethane type epoxy resin and a triphenolethane type epoxy resin, or a mixture thereof.
In the epoxy resin (1), a mixing mass proportion of the epoxy resin (1-1) which is liquid in a temperature range of 0 to 50xc2x0 C. to the epoxy resin (1-2) which is solid in a temperature range of 0 to 50xc2x0 C. is expressed by (1-1:1-2) and falls preferably in a range of (5:95) to (70:30), more preferably (10:90) to (40:60).
The epoxy resin (1) is a resin having a polystyrene-reduced mass average molecular weight falling preferably in a range of 7000 or less, more preferably 150 to 3000 and most preferably 350 to 2000, which is determined by means of a gel permeation chromatography (hereinafter referred to merely as GPC).
The polystyrene-reduced mass average molecular weight determined by means of GPC is controlled to 7000 or less, whereby a viscosity of the composition obtained by an E type viscometer after heat treatment at 80 to 100xc2x0 C. for 20 minutes can be controlled to 50 to 10000 Paxc2x7s at 80 to 100xc2x0 C., and the single layer press hot press bonding aptitude can be improved further more. On the other hand, the polystyrene-reduced mass average molecular weight is controlled to 150 or more, whereby a cross-linking density of the resulting cured matter can be maintained high, and the reliability of heat resistant sealing can be secured. Accordingly, such molecular weight is preferred.
A content of the epoxy resin (1) is 20 to 88.9 mass %, preferably 30 to 70 mass % based on the liquid crystal sealant composition.
In the following epoxy resins, allowed to be used as well are epoxy resins which are directly synthesized or resins which are refined or highly purified, so that they satisfy the requisites described above. Any method can be used as the refining method as long as refining can be carried out so that an ionic conductivity of extract water obtained by contacting and mixing the resin with the same mass of purified water for 10 to 30 minutes falls in the prescribed range. It includes, for example, a water washing-solvent extraction refining method, a ultrafiltration method and a distillation refining method.
 less than Monofunctional Epoxy Resin greater than 
The monofunctional epoxy resin used in the present invention includes, for example, aliphatic monoglycidyl ether compounds, alicyclic monoglycidyl ether compounds, aromatic monoglycidyl ether compounds, aliphatic monoglycidyl ester compounds, aromatic monoglycidyl ester compounds, alicyclic monoglycidyl ester compounds, nitrogen-containing monoglycidyl ether compounds, monoglycidylpropylpolysiloxane compounds and monoglycidylalkanes. It goes without saying that monofunctional epoxy resins other than these resins may be used.
(Aliphatic Monoglycidyl Ether Compound)
Included are, for example, aliphatic monoglycidyl ether compounds obtained by a reaction of polyalkylene glycol monoalkyl ethers having an alkyl group having 1 to 6 carbon atoms with epichlorohydrin and aliphatic monoglycidyl ether compounds obtained by a reaction of aliphatic alcohols with epichlorohydrin.
The polyalkylene glycol monoalkyl ethers having an alkyl group having 1 to 6 carbon atoms include ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, triethylene glycol monoalkyl ethers, polyethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ethers, tripropylene glycol monoalkyl ethers and polypropylene glycol monoalkyl ethers.
Aliphatic alcohols include, for example, n-butanol, isobutanol, n-octanol, 2-ethylhexyl alcohol, dimethylolpropane monoalkyl ethers, trimethylolpropane dialkyl ethers, glycerin dialkyl ethers, dimethylolpropane monoalkyl esters, trimethylolpropane dialkyl esters and glycerin dialkyl esters.
(Alicyclic Monoglycidyl Ether Compound)
Included are, for example, alicyclic monoglycidyl ether compounds obtained by a reaction of alicyclic alcohols having a saturated cyclic alkyl group having 6 to 9 carbon atoms with epichlorohydrin.
The alicyclic alcohols used for the reaction include cyclohexanol and the like.
(Aromatic Monoglycidyl Ether Compound)
Included are, for example, aromatic monoglycidyl ether compounds obtained by a reaction of aromatic alcohols with epichlorohydrin.
The aromatic alcohols used for the reaction include phenol, methylphenol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, benzyl alcohol, t-butylphenol, xylenol and naphthol.
(Aliphatic or Aromatic Monoglycidyl Ester Compound)
Included are, for example, aliphatic monoglycidyl ester compounds or aromatic monoglycidyl ester compounds obtained by a reaction of aliphatic dicarboxylic acid monoalkyl esters or aromatic dicarboxylic acid monoalkyl esters with epichlorohydrin.
 less than Multifunctional Epoxy Resin greater than 
A multifunctional epoxy resin is an epoxy resin having usually 2 to 6 epoxy groups on an average in a molecule, but epoxy resins having more epoxy groups can be used as well, as long as the effects of the present invention are not damaged.
The multifunctional epoxy resin includes, for example, aliphatic polyglycidyl ether compounds, aromatic polyglycidyl ether compounds, trisphenol type polyglycidyl ether compounds, hydroquinone type polyglycidyl ether compounds, resorcinol type polyglycidyl ether compounds, aliphatic polyglycidyl ester compounds, aromatic polyglycidyl ester compounds, aliphatic polyglycidyl etherester compounds, aromatic polyglycidyl etherester compounds, alicyclic polyglycidyl ether compounds, aliphatic polyglycidyl amine compounds, aromatic polyglycidyl amine compounds, hydantoin type polyglycidyl compounds, biphenyl type polyglycidyl compounds, novolak type polyglycidyl ether compounds and epoxidized diene polymers. It goes without saying that multifunctional epoxy resins and modified epoxy resins other than these compounds can be used as well. The compounds, the resins and the modified resins each described above may be used alone or in combination of a plurality thereof.
(Aliphatic Polyglycidyl Ether Compound)
Included are, for example, aliphatic polyglycidyl ether compounds obtained by a reaction of polyalkylene glycols or polyhydric alcohols with epichlorohydrin.
The polyalkylene glycols used for the reaction include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol.
The polyhydric alcohols used for the reaction include dimethylolpropane, trimethylolpropane, spiroglycol and glycerin.
(Aromatic Polyglycidyl Ether Compound)
Included are, for example, aromatic polyglycidy ether compounds obtained by a reaction of aromatic diols with epichlorohydrin.
The aromatic diols used for the reaction include, for example, bisphenol A, bisphenol S, bisphenol F and bisphenol AD.
(Trisphenol Type Polyglycidyl Ether Compound)
Included are, for example, trisphenol type polyglycidyl ether compounds obtained by a reaction of trisphenols with epichlorohydrin.
The trisphenols used for the reaction include 4,4xe2x80x2,4xe2x80x3-methylidenetrisphenol, 4,4xe2x80x2,4xe2x80x3-methylidenetris(2-methylphenol), 4,4xe2x80x2-[(2-hydroxyphenyl)methylene]bis-[2,3,6-trimethylphenol], 4,4xe2x80x2,4xe2x80x3-ethylidenetrisphenol, 4,4xe2x80x2-[(2-hydroxyphenyl)methylene]bis[2-methylphenol], 4,4xe2x80x2-[(2-hydroxyphenyl)ethylene]bis[2-methylphenol], 4,4xe2x80x2-[(4-hydroxyphenyl)methylene]bis[2-methylphenol], 4,4xe2x80x2-[(4-hydroxyphenyl)ethylene]bis[2-methylphenol], 4,4xe2x80x2-[(2-hydroxyphenyl)methylene]bis[2,6-dimethylphenol], 4,4xe2x80x2-[(2-hydroxyphenyl)ethylene]bis[2,6-dimethylphenol], 4,4xe2x80x2-[(4-hydroxyphenyl)methylene]bis[2,6-dimethylphenol], 4,4xe2x80x2-[(4-hydroxyphenyl)ethylene]bis[2,6-dimethylphenol], 4,4xe2x80x2-[(2-hydroxyphenyl)methylene]bis[3,5-dimethylphenol], 4,4xe2x80x2-[(2-hydroxyphenyl)ethylene]bis[3,5-dimethylphenol], 4,4xe2x80x2-[(3-hydroxyphenyl)methylene]bis[2,3,6-trimethyl-phenol], 4,4xe2x80x2-[(4-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol], 4,4xe2x80x2-[(2-hydroxyphenyl)methylene]bis-[2-cyclohexyl-5-methylphenol], 4,4xe2x80x2-[(3-hydroxyphenyl)-methylene]bis-[2-cyclohexyl-5-methylphenol], 4,4xe2x80x2-[(4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol], 4,4xe2x80x2-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenol-ethylidene]bisphenol], 4,4xe2x80x2-[(3,4-dihydroxyphenyl)-methylene]bis[2-methylphenol], 4,4xe2x80x2-[(3,4-dihydroxyphenyl)methylene]bis[2,6-dimethylphenol], 4,4xe2x80x2-[(3,4-dihydroxyphenyl)methylene]bis[2,3,6-trimethylphenol] and 4-[bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)methyl]-1,2-benzenediol.
(Hydroquinone Type Polyglycidyl Ether Compound)
Included are, for example, hydroquinone type polyglycidyl ether compounds obtained by a reaction of hydroquinone with epichlorohydrin.
(Resorcinol Type Polyglycidyl Ether Compound)
Included are, for example, resorcinol type polyglycidyl ether compounds obtained by a reaction of resorcinol with epichlorohydrin.
(Aliphatic Polyglycidyl Ester Compound)
Included are, for example, aliphatic polyglycidyl ester compounds obtained by a reaction of aliphatic dicarboxylic acids represented by adipic acid with epichlorohydrin.
(Aromatic Polyglycidyl Ester Compound)
Included are, for example, aromatic polyglycidyl ester compounds obtained by a reaction of aromatic polycarboxylic acids with epichlorohydrin.
The aromatic polycarboxylic acids used for the reaction include, for example, isophthalic acid, terephthalic acid and pyromellitic acid.
(Aliphatic or Aromatic Polyglycidyl Etherester Compound)
Included are, for example, aliphatic polyglycidyl etherester compounds or aromatic polyglycidyl etherester compounds obtained by a reaction of hydroxydicarboxylic acid compounds with epichlorohydrin.
(Alicyclic Polyglycidyl Ether Compound)
Included are, for example, alicyclic polyglycidyl ether compounds represented by dicyclopentadiene type polyglycidyl ether compounds.
(Aliphatic Polyglycidyl Amine Compound)
Included are, for example, aliphatic polyglycidyl amine compounds obtained by a reaction of aliphatic polyamines represented by ethylenediamine, diethylenetriamine and triethylenetetraamine with epichlorohydrin.
(Aromatic Polyglycidyl Amine Compound)
Included are, for example, aromatic polyglycidyl amine compounds obtained by a reaction of aromatic amines represented by diaminodiphenylmethane, aniline and metaxylilenediamine with epichlorohydrin.
(Hydantoin Type Polyglycidyl Compound)
Included are, for example, hydantoin type polyglycidyl compounds obtained by a reaction of hydantoin and derivatives thereof with epichlorohydrin.
(Novolak Type Polyglycidyl Ether Compound)
Included are, for example, novolak type polyglycidyl ether compounds obtained by a reaction of novolak resins derived from formaldehyde and aromatic alcohols represented by phenol, cresol and naphthol with epichlorohydrin. Further, representative examples thereof include, for example, modified phenol novolak resins obtained by a reaction of modified phenol resins which are derived from phenol and p-xylylenedichloride and in which a phenol nucleus and a paraxylene nucleus are combined with a methylene bond with epichlorohydrin.
(Epoxidized Diene Polymer)
Included are, for example, epoxidized polybutadiene and epoxidized polyisoprene.
 less than Modified Epoxy Resin greater than 
Representative are addition derivative compositions comprising at least one selected from the epoxy resins described above and at least one selected from amine compounds, mercapto compounds and carboxyl compounds. The above addition derivative compositions are preferably those which do not separate into phases per se and which are liquid or solid at room temperature.
Specific examples of the amine compounds, the mercapto compounds and the carboxyl compounds which are suitably used for producing the modified epoxy resins shall be given below respectively.
[Amine Compound]
Given as representative examples thereof are, for example, aliphatic amines, alicyclic amines, aromatic amines, polyamides, polyamideamines, cyanamides, amino group-containing low molecular polysiloxanes, amino group-containing low molecular butadiene-acrylonitrile copolymers and amino group-containing low molecular acryl compounds.
(Aliphatic Amines)
They shall not specifically be restricted as long as they are aliphatic amine monomers. They are represented by, for example, monoethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, triethylenetetraamine, hexamethylenediamine, propylenediamine, dipropylenetriamine, polyethylene glycol monoamine, polyethylene glycol diamine, polypropylene glycol monoamine and polypropylene glycol diamine.
(Alicyclic Amines)
They shall not specifically be restricted as long as they are alicyclic amine monomers. Representative are, for example, isophoronediamine, cyclohexyldiamine, norbornanediamine, piperidine, bisaminopropyltetraoxaspiroundecane and modified polyamines thereof.
(Aromatic Amines)
They shall not specifically be restricted as long as they are aromatic amine monomers. Representative are, for example, phenylenediamine, xylylenediamne, diaminodiphenylmethane, diaminodiphenylsulfone and modified polyamines thereof.
(Polyamides)
They may be any ones as long as they are polyamides and shall not specifically be restricted. They are represented by, for example, dehydrated condensed derivatives of at least one polyamine compound selected from the aliphatic amines, the alicyclic amines and the aromatic amines each described above with dicarboxylic acid compounds.
(Polyamideamines)
They may be any ones as long as they are polyamideamines and shall not specifically be restricted. They are represented by, for example, dehydrated condensed derivatives of at least one amine selected from the aliphatic amines, the alicyclic amines and the aromatic amines each described above with dicarboxylic acid compounds or aminocarboxylic acid compounds.
(Cyanamides)
They may be any ones as long as they are cyanamides and shall not specifically be restricted. They are represented by, for example, dicyanediamide.
(Amino Group-containing Low Molecular Polysiloxanes)
They may be any ones as long as they are amino group-containing low molecular polysiloxanes and shall not specifically be restricted. They are represented by, for example, polysiloxanes having an amino group at both ends and having an amine equivalent of 2000 or less. (Amino group-containing Low Molecular Butadiene-acrylonitrile Copolymers)
They may be any ones as long as they are amino group-containing low molecular butadiene-acrylonitrile copolymers and shall not specifically be restricted. They are represented by, for example, butadiene-acrylonitrile copolymers having an amino group at both ends and having an amine equivalent of 2000 or less and an acrylonitrile monomer-reduced content of 16 to 30 mass %.
(Amino Group-containing Low Molecular Acryl Compounds)
They may be any ones as long as they are amino group-containing low molecular acryl compounds and shall not specifically be restricted. They are represented by, for example, polyamino group-containing acryl compounds having an amine equivalent of 2000 or less and an SP value (solubility parameter) of 8.5 to 10 which is a barometer of affinity.
[Mercapto compound]
It may be any ones as long as it is a mercapto compound and shall not specif ically be restricted. Given as examples thereof are, for example, MR-6 and MR-7 which are products manufactured by Mitsui Chemicals Inc. and polysiloxanes having a mercapto group at both ends and having an amine equivalent of 2000 or less.
[Carboxyl Compounds]
They may be any ones as long as they are carboxylic acid monomers and/or polycarboxylic acid compounds and shall not specifically be restricted. Given as representative examples thereof are, for example, carboxylic acid monomers having 20 or less carbon atoms represented by maleic acid, maleic acid anhydride, itaconic acid, adipic acid, trimellitic acid, trimellitic acid anhydride, phthalic acid, phthalic acid anhydride, tetrahydrophthalic acid, tetrahydrophthalic acid anhydride, himic acid, nadic acid anhydride and glutaric acid anhydride, and polyesters having an acid group at an end derived from them and dihydroxy compounds.
Another examples thereof include polysiloxanes, butadiene-acrylonitrile copolymers and low molecular acryl compounds each of which has a carboxyl group at both ends and has an acid value of 5 to 100 mg KOH/g.
In the liquid crystal sealant composition of the present invention, the epoxy resin (1) alone has preferably a viscosity by an E type viscometer of not less than 0.3 Paxc2x7s at 80xc2x0 C. It falls more preferably in a range of 1 Paxc2x7s or more, particularly preferably 5 to 1000 Paxc2x7s. If the epoxy resin (1) alone has a viscosity by an E type viscometer of more than 0.3 Paxc2x7s at 80xc2x0 C., the single layer hot press aptitude of the liquid crystal sealant composition is elevated.
In the liquid crystal sealant composition of the present invention, contained is 1 to 15 mass % of the rubber-like polymer fine particle (2) which has a softening point of 0xc2x0 C. or lower in terms of a softening point determined by means of a torsional braid analyzer (hereinafter referred to merely as TBA) called a torsional pendulum method and which has a primary particle average diameter of 5 xcexcm or less determined by electron microscope observation (hereinafter referred to merely as the rubber-like polymer fine particle).
The rubber-like polymer fine particle has more preferably an average primary particle diameter of 0.01 to 5 xcexcm, further preferably 0.01 to 3 xcexcm and particularly preferably 0.05 to 2 xcexcm.
The rubber-like polymer fine particle is used in a proportion of 1 mass % or more in the liquid crystal sealant composition of the present invention, whereby a relaxation effect of a residual distortion in a liquid crystal display element itself produced with using the liquid crystal sealant composition of the present invention is derived, and as a result, the adhesion reliability can be raised. Accordingly, such proportion is preferred. On the other hand, this is controlled to 15 mass % or less, whereby the heat resistant rigidity required to the cured matter can be preferably secured. It is added more preferably in a range of 3 to 12.5 mass %. In particular, the rubber-like polymer fine particle (2) accounts more preferably for 5 to 10 mass % in terms of a proportion based on the liquid crystal sealant composition.
Also, the softening point of the rubber-like polymer fine particle (2) is controlled to 0xc2x0 C. or lower, whereby the adhesion reliability tends to be raised more at a low temperature, and therefore it is preferred. Further, the primary particle diameter of the rubber-like polymer fine particle (2) is controlled to 5 xcexcm or less, whereby a gap in the liquid crystal cell can be thinned, and a use amount of expensive liquid crystal can be controlled. In addition thereto, the liquid crystal display response speed can be improved as well.
The preferred rubber-like polymer fine particle (2) includes a silicone rubber fine particle and/or an acryl rubber fine particle or a polyolefin rubber fine particle each having a softening point of xe2x88x9230xc2x0 C. or lower and a primary particle diameter of 0.01 to 3 xcexcm, and the rubber-like polymer fine particle is more preferably a cross-linking rubber particle.
The following known rubber-like polymers can suitably be selected and used for these rubber-like polymer fine particles as long as they have a softening of 0xc2x0 C. or lower.
Given as examples thereof are, for example, rubber-like polymers of an acryl rubber base, rubber-like polymers of a silicone rubber base, rubber-like polymers of a conjugated diene rubber base, rubber-like polymers of an olefin rubber base, rubber-like polymers of a polyester rubber base, rubber-like polymers of a urethane rubber base, composite rubber and rubber-like polymers having a functional group reacting with an epoxy group. In particular, these rubber-like polymers have preferably a functional group reacting with an epoxy group.
These rubber-like polymers (2) used for the liquid crystal sealant composition may be used alone or in combination of a plurality thereof.
Specific examples of these rubber-like polymer fine particles shall be shown below.
 less than Rubber-like Polymer Fine Particle of an Acryl Rubber Base greater than 
Specific examples of the rubber-like polymer fine particle of an acryl rubber base include, for example, a method using particles obtained by drying a core/shell type emulsion in which a core part comprises acryl rubber, a method using in the form of a resin composition obtained by subjecting an acryl base monomer to non-aqueous dispersion polymerization in an epoxy resin and a method using in the form of a resin composition obtained by preparing separately a solution of an acryl rubber polymer into which a functional group reacting with an epoxy group is introduced, and then pouring or dropwise adding it into an epoxy resin to mechanically mix, followed by removing the solvent from the solution or grafting the acryl rubber to the epoxy resin to stably disperse acryl rubber fine particles in the epoxy resin.
 less than Rubber-like Polymer Fine Particle of a Silicone Rubber Base greater than 
Specific examples of the rubber-like polymer fine particle of a silicone rubber base include, for example, a method using powdery silicone rubber fine particles and a method using in the form of a resin composition obtained by introducing a double bond into an epoxy resin, reacting the epoxy resin with a silicone macro monomer having an acrylate group at a single end which is capable of reacting with the double bond and then charging vinyl silicone and hydrogen silicone into the reaction product to dispersion polymerize. Also, it includes a method using in the form of a resin composition obtained by reacting a reactive silicone oil in which a functional group capable of reacting with an epoxy group is introduced into both ends thereof and which has a molecular weight of 10,000 to 300,000. Further, other silicone rubber-like polymers can be used as well without any specific restrictions.
 less than Rubber-like Polymer Fine Particle of a Conjugated Diene Rubber Base greater than 
Specific examples of the rubber-like polymer fine particle of a conjugated diene rubber base include, for example, conjugated diene rubber-like polymer fine particles obtained by polymerizing or copolymerizing monomers such as 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene and chloroprene. They shall not specifically be restricted, and commercial products may be used as they are. More specific examples of the conjugated diene rubber include a copolymer of butadiene with acrylonitrile, a copolymer of butadiene with acrylonitrile having a carboxyl group at an end and a copolymer of butadiene with acrylonitrile having an amino group at an end.
 less than Rubber-like Polymer Fine Particle of an Olefin Rubber Base greater than 
Specific examples of the rubber-like polymer fine particle of an olefin rubber base include, for example, fine particles comprising amorphous homopolymers of ethylene, propylene, 1-butene, 2-butene and isobutene, or copolymers or terpolymers thereof with other copolymerizable monomers, or compositions thereof. A good example is a method using in the form of a resin composition obtained by subjecting a product commercially available in the form of an olefin rubber latex to dehydrating treatment in an epoxy resin to disperse and stabilize the olefin rubber in the epoxy resin.
 less than Rubber-like Polymer Fine Particle of a Polyester Rubber Base greater than 
The rubber-like polymer fine particle of a polyester rubber base is a fine particle comprising a rubber-like polymer having a polyester bond in a polymer skeleton and shall not specifically be restricted. Specific examples of the polyester rubber include, for example, low softening point polyester rubbers derived from at least one diol component selected from liquid polysiloxanediol, liquid polyolefindiol, polypropylene glycol and polybutylene glycol, if necessary, in the presence of triol or a polyhydric alcohol compound which has more hydroxyl groups than triol and at least one dibasic acid selected from adipic acid, maleic acid, succinic acid and phthalic acid, low softening point polyester rubbers prepared by substituting acid anhydrides for the dibasic acids described above or low softening point polyester rubbers derived from hydroxypolycarboxylic acids and the like.
 less than Rubber-like Polymer Fine Particle of a Urethane Rubber Base greater than 
The rubber-like polymer fine particle of a urethane rubber base is a fine particle comprising a rubber-like polymer having a urethane bond and/or a urea bond in a rubber-like polymer skeleton and shall not specifically be restricted. Specific examples of the urethane rubber include, for example, rubber-like polyurethanes obtained by reacting at least one diol component selected from liquid polysiloxanediol, liquid polyolefiridiol, polypropylene glycol and polybutylene glycol, if necessary, in the presence of triol or a polyhydric alcohol compound which has more hydroxyl groups than triol with a diisocyanate compound represented by hexamethylenediisocyanate, isophoronediisocyanate, tolylenediisocyanate, diphenylmethanediisocyanate and norbornanediisocyanate, and rubber-like polyurethanes obtained by reacting at least one long chain diamine component selected from liquid polysiloxanediamine (the amino group-containing low molecular polysiloxane described above), liquid polyolefindiamine and polypropylene glycoldiamine, if necessary, in the presence of triamine or a polyamine compound which has more amino groups than triamine with a diisocyanate compound represented by hexamethylenediisocyanate, isophoronediisocyanate, tolylenediisocyanate, diphenylmethanediisocyanate and norbornanediisocyanate.
 less than Composite Rubber Particle greater than 
Given as examples of the composite rubber are, for example, fine particles comprising graft polymers and/or block polymers or core/shell polymers and composite polymers each comprising two or more kinds of the acryl base, the silicone base, the conjugated diene base, the olefin base, the polyester base and the urethane base each described above.
 less than Rubber-like Polymer Having a Functional Group Reacting With an Epoxy Group  greater than 
Representative examples of the rubber-like polymer having a functional group reacting with an epoxy group include, for example, particles obtained by introducing functional groups reacting with an epoxy group into rubber like polymers of the acryl base, the silicone base, the conjugated diene base, the olefin base, the polyester base and the urethane base each described above.
The functional group reacting with an epoxy group includes, for example, a mercapto group, an amino group, an imino group, a carboxyl group, an acid anhydride group, an epoxy group and a hydroxyl group.
At least one of these functional groups is preferably introduced into the rubber-like polymer in a proportion of preferably 0.01 to 25 mass %, more preferably 0.1 to 10 mass %;
A method for introducing these functional groups shall not specifically be restricted and may be any one of an introducing methods comprising a random copolymerization method, an alternate copolymerization method, a condensation polymerization method, an addition polymerization method and a core-shell polymerization method in each of which a functional group-containing. monomer is polymerized with a monomer to constitute a main chain polymer, an ion adsorption-introducing method, a swelling impregnation-introducing method and a method for graft-polymerizing with a polymer forming a rubber-like polymer.
Among them, the copolymerizing method and the graft-polymerizing method are preferred since necessary functional groups can efficiently be introduced into the vicinity of a rubber-like polymer fine particle surface in the smaller amount.
In this rubber-like polymer having a functional group reacting with an epoxy group, a structure originating in a monomer having a functional group reacting with an epoxy group accounts preferably for 0.1 to 25 mass % in terms of a weight proportion based on the rubber-like polymer.
An adhesive property of the resulting liquid crystal sealant composition is notably improved by controlling the content of the repetitive structure originating in the monomer having a functional group reacting with an epoxy group to 0.1 mass % or more and 25 mass % or less. Accordingly, such content is preferred.
In the liquid crystal sealant composition of the present invention, the rubber-like polymer fine particle (2) preferably takes the form of a particle in the epoxy resin. A method for finding that the rubber-like polymer is present in the form of a particle in the epoxy resin shall not specifically be restricted, and being suitably employed are, for example, a method in which a mixture of the epoxy resin (1) having no turbidity and the rubber-like polymer fine particles (2) is prepared and the composition is observed under an optical microscope to confirm the presence of rubber-like polymer fine particles, a method in which a required amount of a polymercaptan base curing agent or a polyamine base curing agent each of which is used at room temperature is added to the composition to obtain a cured matter and a minute cutting plane thereof is sensitized by dyeing with osmic acid to be observed under a transmission electron microscope (TEM) or a scanning electron microscope (SEM) and a method for finding by measuring microscopic infrared absorption spectra of a micro layer of the cured matter (hereinafter referred to merely as microscopic IR measurement).
A method for judging that the rubber-like polymer fine particle (2) is present in the form of a fine particle in the liquid crystal sealant composition of the present invention shall not specifically be restricted, and being suitably employed are, for example, a method in which the thermally cured matter thereof is produced and then a minute cutting plane thereof is sensitized by dyeing with osmic acid to be observed under TEM or SEM, a method for judging by observing a broken section of the cured matter obtained in the same manner under SEM and comparing it with the image of element distribution analysis, a method in which a cured matter surface is subjected to etching after provided with selectivity by a known method and then observed under TEM or SEM, a method for judging by subjecting a micro layer of the cured matter to microscopic IR measurement and a method in which a micro layer of the cured matter is irradiated with a heat ray to judge kinds thereof from the generated gas components as well as particle diameters thereof.
Also, a method for determining a blending amount of the rubber-like polymer fine particles (2) contained in the liquid crystal sealant composition prepared shall not specifically be restricted, and allowed to be suitably employed are, for example, a method in which infrared absorption spectra (IR) of the liquid crystal sealant composition are taken to determine the amount from the calibration curves of the absorption spectra specific to a rubber-like polymer fine particle, a method in which the kind of the rubber-like polymer fine particle specified by IR analysis is identified to determine it from a value of an elastic modulus attenuation factor [Gxe2x80x3] in a low temperature area by TBA measurement as an index for an effect which is definitely revealed depending on the kind of the rubber-like polymer fine particle, a thermal decomposition gas chromatography method, an elemental analysis method, a method in which a rubber-like polymer fine particle-occupying volume is determined from plural TEM or SEM photographs of the cured matter to calculate the amount by specific gravity reduction and a method for determining by analysis of thermally decomposed gas components.
The rubber-like polymer fine particles (2) may or may not be grafted in advance to the epoxy resin (1) in the liquid crystal sealant composition of the present invention.
The inorganic filler (3) used in the present invention may be any one as long as they can usually be used as an inorganic filler in the electronic material field.
To be specific, they include, for example, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, asbestos powder, quartz powder, mica and glass fiber.
A total content of alkali metals which is determined by an atomic absorption spectrometry of the inorganic filler decomposition products under a wet condition is controlled preferably to 50 ppm or less, more preferably 30 ppm or less and particularly preferably 15 ppm or less. This makes it possible to avoid a free ion from unnecessarily transferring to the liquid crystal phase at the time of bringing liquid crystal into contact with the cured matter of the crystal sealant composition of the present invention. A refining method for controlling the total content of alkali metals to 50 ppm or less shall not specifically be restricted, and the refining may be carried out by a known method such as an ion exchange method for an aqueous solution of the raw materials.
Also, the inorganic filler (3) has preferably a particle diameter falling in a range of 5 xcexcm or less of a value at 99 mass % on a weight integration curve, which is determined by means of a laser particle size-measuring instrument using laser having a wavelength of 632.8 nm, and it has more preferably a weight average particle diameter falling in a range of 0.005 to 1 xcexcm, which is shown by a value at 50 mass % on the weight integration curve.
In general, use of the inorganic filler having a particle diameter of 5 xcexcm or less of a value at 99 mass % on the weight integration curve elevates further more dimensional stability of a gap width in the liquid crystal panel and therefore is preferred.
In the liquid crystal sealant composition of the present invention, a content of the inorganic filler (3) is 5 to 50 mass %. It falls more preferably in a range of 5 to 30 mass %, particularly preferably 5 to 15 mass %. The content controlled to 5 mass % or more makes it possible to maintain a coated form-holding property in screen printing or dispenser coating. On the other hand, the content controlled to 50 mass % or less makes it possible to optimize a viscosity of the liquid crystal sealant composition and secure the coating workability.
The inorganic filler (3), though not specifically restricted, is preferably used after modified in advance by grafting with an epoxy resin (1) and a silane coupling agent (6).
In modification by grafting, a part or the whole of the inorganic filler (3) may be modified by grafting. In this case, the grafting rate is shown by a mass increasing rate determined by a repetitive solvent-washing method, and usually either or both of the epoxy resin (1) and the silane coupling agent (6) of 1 to 50 mass parts per 100 mass parts of the inorganic filler (3) are preferably chemically bonded.
A method for measuring the content of the inorganic filler (3) contained in the liquid crystal sealant composition shall not specifically be restricted and may be an optional method such as a method for determining by elemental analysis, a method for determining by fluorescent X-ray analysis and a method for determining by a heat decomposition residual amount.
A compound which can allow an epoxy resin to cause a curing reaction by heating at 50xc2x0 C. or higher can be selected and used as the thermally active potential curing agent for epoxy resin (4) used in the present invention.
The composed shall not specifically be restricted and includes, for example, dicyandiamides and derivatives thereof, dihydrazide compounds such as adipic acid dihydrazide and isophthalic acid dihydrazide, 4,4xe2x80x2-diaminodiphenylsulfone, imidazole derivatives such as 2-n-pentadecylimidazole, complexes of imidazole compounds represented by 2-methylimidazole and 2-ethyl-4-methylimidazole and aromatic acid anhydrides, adducts of imidazole compounds and epoxy resins and modified derivatives thereof, adducts of urea and/or thiourea compound and epoxy resins or diisocyanate compounds, boron trifluoride-amine complexes, vinyl ether-blocked carboxylic acid compounds, aromatic allyl ether compounds represented by allyl ether compounds of 1,6-dinaphthol, N,N-dialkylurea derivatives, N,N-dialkylthiourea derivatives, melamine and guanamine.
The thermally active potential curing agent for epoxy resin (4) accounts for 5 to 30 mass % in terms of a proportion based on the liquid crystal sealant composition of the present invention. The proportion controlled to 5 mass % or more can control curing of the liquid crystal sealant composition of the present invention within required time. On the other hand, the proportion controlled to 30 mass % or less can reduce the presence of the unreacted curing agent to a lower level.
A method for determining a content of the thermally active potential curing agent for epoxy resin in the liquid crystal sealant composition includes preferably a method in which it is determined from infrared spectra, a method in which it is determined by analysis of a functional group and a method of NMR analysis for a solid.
In the liquid crystal sealant composition of the present invention, the high softening point-polymer fine particle (5) is added in a range of 0.1 to 9.5 mass % in terms of a proportion based on the composition. Use of 0.1 mass % or more makes it possible to elevate the seal adhesion characteristic in which seal leak and bleeding are not caused at a primary bonding step by a single layer hot press and therefore is preferred. On the other hand, use of 9.5 mass % or less makes it possible to sufficiently secure the gap-forming workability and therefore is preferred.
The high softening point-polymer fine particle (5) is the high softening point-polymer fine particle (5) (hereinafter referred to merely as the high softening point-polymer fine particle) having a softening point of 50xc2x0 C. or higher in terms of a softening point determined by TBA and an average particle diameter of a primary particle of 2 xcexcm or less determined by observation under an electron microscope.
The gap-forming workability can be secured by controlling the average particle diameter of the primary particle of the high softening point-polymer fine particle (5) to 2 xcexcm or less. The average particle diameter of the primary particle falls more preferably in a range of 0.01 to 1 xcexcm, further more preferably 0.2 to 0.5 xcexcm.
The high softening point-polymer fine particle (5) of either a cross-linking type or a non-cross-linking type can be used, and the cross-linking type is more preferred. In particular, the high softening point-polymer micro particle having a micro cross-linking structure is most preferred.
The high softening point-polymer fine particle having a micro cross-linking structure can be produced by controlling a cross-linkable monomer to a range of 0.1 to 50 mass %, preferably 1 to 10 mass % and most preferably 1 to 3 mass % based on the whole monomers for producing the polymer.
A gel content is one of indices for a degree of the micro cross-linking. This is an index determined from the following equation, wherein 10 g of the high softening point-polymer fine particle is dispersed in 50 g of a methylcarbitol solvent and stirred for one hour at 25xc2x0 C., and then it is filtered to determine a quantity of filtrate and a polymer content (dissolved amount) in the filtrate:
gel content (%)=(dissolved amount/10 g)xc3x97100
This gel content index falls preferably in a range of 0 to 50%, more preferably 0 to 5%.
The high softening point-polymer fine particle falls preferably in a range of 9 to 11, more preferably 9.3 to 10.5 in terms of an SP value (solubility parameter) which is an index for showing an affinity calculated from a chemical structural formula.
Given as specific examples of the high softening point-polymer fine particle (5) are, for example, polymers having micro cross-linking polymethyl methacrylate as the main component which is obtained by copolymerizing 0.1 to 50 mass % of cross-linkable monomers and polymethyl methacrylate polymers having an monomer structure falling in a range of 0.1 to 50, mass %. The high softening point-polymer fine particle (5) has preferably a softening point of 60 to 150xc2x0 C. and a primary particle diameter falling in a range of 0.01 to 3 xcexcm.
In this high softening point-polymer fine particle, one kind of a functional group such as an epoxy group, an amino group, an imino group, a mercapto group and a carboxyl group is more preferably introduced into a particle surface thereof.
In the liquid crystal sealant composition of the present invention, the rubber-like polymer fine particle (2) and the high softening point-polymer fine particle (5) may be combined in advance, and included is, for example, an embodiment in which the rubber-like polymer fine particle (2) described above forms a core phase and the high softening point-polymer fine particle (5) forms a shell phase, a so-called core/shell type composite fine particle of (2) and (5) (A). Also, in contrast with this, allowed to be used is a core/shell type composite fine particle (B) in which the high softening point-polymer fine particle (5) forms a core phase and the rubber-like polymer fine particle (2) forms a shell phase. When used in a combined form, the former core/shell type composite fine particle (A) is preferably used.
In the core/shell type composite fine particle (A) containing the rubber-like polymer fine particle (2) as the core phase, a mass ratio of core:shell falls preferably in a range of (1:0.3) to (1:2). For example, a brand name ┌Zeon F-351┘, a product manufactured by Nippon Zeon Co., Ltd. can readily be available as a specific example of the core/shell type high softening point-polymer fine particle (A) and can preferably be used.
A method for determining a proportion ofxe2x80x2the high softening point-polymer fine particle (5) contained in the liquid crystal sealant composition shall not specifically be restricted and includes, for example, a thermal decomposition gas chromatography method and a nuclear magnetic resonance spectrum (NMR) method.
In the liquid crystal sealant composition of the present invention, allowed to be added are 0.1 to 5 mass parts of the silane coupling agent (6) and 0.1 to 10 mass parts of the curing accelerator (7) per 100 mass parts of the composition comprising the components (1) to (5). The silane coupling agent (6) and the curing accelerator (7) which can be used in this case shall be described below in detail.
The silane coupling agent (6) shall not specifically be restricted,h and any one can be used. Trialkoxysilane compounds and methyldialkoxysilane compounds can be given as preferred examples thereof. Given-as specific examples thereof are xcex3-glycidoxypropylmethyldimethoxysilane, xcex3-glycidoxy-propyltrimethoxysilane, xcex3-glycidoxypropylmethyldiethoxy-silane, xcex3-glycidoxypropyltriethoxysilane, xcex3-aminopropyl-methyldimethoxysilane, xcex3-aminopropyltrimethoxysilane, xcex3-aminopropylmethyldiethoxysilane xcex3-aminopropyltriethoxysilane, N-aminoethyl-xcex3-aminopropylmethyldimethoxysilane, N-aminoethyl-xcex3-aminopropyltrimethoxysilane, N-aminoethyl-xcex3-aminopropyltriethoxysilane , N-phenyl-xcex3-amino-propyltrimethoxysilane, N-phenyl-xcex3-aminopropyltriethoxy-silane, N-phenyl-xcex3-aminopropylmethyldimethoxysilane, N-phenyl-xcex3-aminopropylmethyldiethoxysilane, xcex3-mercapto-propylmethyldimethoxysilane, xcex3-mercaptopropyltriethoxysilane, xcex3-mercaptopropylmethyldiethoxysilane xcex3-mercaptopropyltrimethoxysilane, xcex3-isocyanatopropylmethyl-diethoxysilane and xcex3-isocyanatopropyltriethoxysilane. Among them, glycidylsilane is particularly preferred.
The silane coupling agent (6) is used preferably in a proportion falling in the range described above, and use of 0.1 mass % or more based on the composition comprising the components (1) to (5) can expect the adhesive property to a glass substrate to be improved. On the other hand, the use in the proportion controlled to 5 mass % or less makes it possible to secure a balance between the non-bleeding property and the adhesion reliability and therefore is preferred. It is used more preferably in a proportion of 0.5 to 3 mass %.
A method for determining a proportion of the silane coupling agent (6) contained in the liquid crystal sealant composition shall not specifically be restricted and includes, for example, a thermal decomposition gas chromatography method, a nuclear magnetic resonance spectrum (NMR) method and a method in which a gas volume generated by hydrolysis is determined.
The curing accelerator (7) which can be used in combination, if necessary, for the liquid crystal sealant composition of the present invention includes, for example, 1,1-dialkylurea derivatives, imidazole derivatives or salts thereof, adducts of polyamine compounds and epoxy resins or salts thereof, adducts of amine compounds and diisocyanate compounds or salts thereof, adducts of amine compounds and diisocyanate compounds or modified derivatives thereof, trisdimethylaminomethylphenol or salts thereof, 1,8-diazabicyclo (5,4,0)-undecene-7 and salts thereof, 1,5-diazabicyclo (4,3,0)-nonene-5 and salts thereof, 6-dibutylamino-1,8-diazabicyclo (5,4,0)-undecene-7 and salts thereof and triphenylphosphine.
The curing accelerator (7) accounts preferably for 0.1 to 10 mass % based on the composition. If it accounts for 0.1 mass % or more, a curing activity of the potential curing agent for epoxy resin (4) can sufficiently be derived in hot curing. On the other hand, if it is used in a proportion of 10 mass % or less, storage stability of the resulting liquid crystal sealant composition at 25xc2x0 C. can be raised.
Among them, those having low activity at a low temperature and high storage stability are preferred, and from this point of view, 1,1-dialkylurea derivatives are preferred.
The sum of the contents of alkali metals determined by an atomic absorption spectrometry of the curing accelerator decomposition products under a wet condition is controlled preferably to 50 ppm or less, more ipreferably 30 ppm or less and particularly preferably to 15 ppm or less. This makes it possible to avoid a free ion from substantially transferring to the liquid crystal phase at the time of bringing liquid crystal into contact with the cured matter of the liquid crystal sealant composition of the present invention. A refining method for controlling the total content of alkali metals to 50 ppm or less shall not specifically be restricted and the refining may be carried out by a known method such as a solvent-extracting refining method.
(1,1-Dialkylurea Derivatives)
Representative examples thereof are, for example, 3-(p-chlorophenyl)-1,1-dimethylurea, 3-(o,p-dichlorophenyl)-1,1-dimethylurea, 2,4-[bis(1,1-dimethylurea)]toluene and 2,6-[bis(1,1-dimethylurea)]toluene.
(Imidazole Derivatives or Salts Thereof)
The imidazole derivatives include, for example, 2-methylisocyanuric acid adducts, 2-n-pentadecylimidazole, N-cyanoethyl-2-ethyl-4-methylimidazole and adducts of imidazole compound and epoxy resins, and they can be used alone or in combination of two or more kinds thereof.
The adducts of imidazole compounds and epoxy resins mean adducts of imidazole compounds having active. hydrogen groups and epoxy resins.
Given as specific examples of the adducts of imidazole compounds and epoxy resins are, for example, adducts having a softening point of 70 to 150xc2x0 C., which comprises reaction products obtained by reacting epoxy resins with imidazole compounds and then further reacting with such amount of phenol novolak resins as does not exceed twice as much as a mass of the epoxy resins and in which a ratio of an epoxy group equivalent in the epoxy resin to a molecular equivalent of the imidazole compound falls in a range of (0.8:1) to (2.2:1). Another preferred specific example includes an adduct obtained by reacting an epoxy resin with an imidazole compound and then further reacting with a hydroxystyrene resin. Further, given as the example thereof is an adduct of an epoxy resin, a compound having a nitrogen-base group having no primary amino group in a molecule (including an imidazole compound) and a phenol-formaldehyde resin having a mass average molecular weight of 2000 to 10000 reduced to polystyrene determined by GPC.
Those having a melting point of 70 to 150xc2x0 C. are particularly preferably selected and used as the adducts of imidazole compounds and epoxy resins.
(Adducts of Polyamine Compounds and Epoxy Resins)
The adducts of polyamine compounds and epoxy resins shall not specifically be restricted and are represented by adducts derived from known polyamine compounds and epoxy resins.
More specific examples thereof include, for example, adducts obtained by reacting addition reaction products of epoxy resins and polyamines with compounds having two or more acidic hydroxyl groups. The compounds having two or more acidic hydroxyl groups includes phenol resins, modified phenol resins and polycarboxylic acids.
(Adducts of Amine Compounds and Diisocyanate Compounds or Modified Derivatives Thereof)
The adducts of amine compounds and diisocyanate compounds are represented by substances obtained by reacting known primary or secondary amine compounds with diisocyanates. Substances obtained by reacting N,N-dialkylaminoalkylamines and cyclic amines with diisocyanates with heating can be given as examples of the modified derivatives of the adducts of amine compounds and diisocyanate compounds. Further, given as the examples thereof are compositions obtained by bringing diisocyanate compounds into even contact with a particle surface of a powdery substance having a softening point of 60xc2x0 C. or higher and a tertiary amino group.
(Trisdimethylaminomethylphenol Salts)
The trisdimethylaminomethylphenol salts include, for example, trisdimethylaminomethylphenol octylic acid salts, trisdimethylaminomethylphenol oleic acid salts and trisdimethylaminomethylphenol formic acid salts.
(1,8-Diazabicyclo (5,4,0)-undecene-7 Salts)
Representative examples of the 1,8-diazabicyclo (5,4,0)-undecene-7 salts (hereinafter referred to merely as DBU salt) include, for example, DBU phenol salt, DBU polyphenol compound salt, DBU polyphenol salt, DBU octylic acid salt, DBU oleic acid salt and DBU formic acid salt.
(1,5-Diazabicyclo (4,3,0)-nonene-5 Salts)
Representative examples of the 1,5-diazabicyclo (4,3,0)-nonene-5 salts (hereinafter referred to merely as DBN salt) include, for example, DBN phenol salt, DBN polyphenol compound salt, DBN polyphenol salt, DBN octylic acid salt, DBN oleic acid salt, DBN formic acid salt and DBN paratoluenesulfonic acid salt.
(6-Dibutylamino-1,8-diazabicyclo (5,4,0)-undecene-7 Salts)
Representative examples of the 6-dibutylamino-1,8-diazabicyclo (5,4,0)-undecene-7 salts (hereinafter referred to merely as DB salt) include, for example, DB phenol salt, DB polyphenol compound salt, DB polyphenol salt, DB octylic acid salt, DB oleic acid salt, DB formic acid salt and DB paratoluenesulfonic acid salt.
In the liquid crystal sealant composition of the present invention, the particularly preferred example of the curing accelerator (7) is one selected from 3-(p-chlorophenyl)-1,1-dimethylurea, 3-(o,p-dichlorophenyl)-1,1-dimethylurea, 2,4-[bis(1,1-dimethylurea)]toluene and 2,6-[bis(1,1-dimethylurea)]toluene.
In the liquid crystal sealant composition of the present invention, 1 to 25 mass % of the solvent (8) which is compatible with an epoxy resin and has a boiling point falling in a range of 150 to 230xc2x0 C. and which is inactive to an epoxy group may be used, if necessary, in any one of the compositions comprising either the component (1) to (5) or (1) to (7). Use of 1 mass % or more thereof elevates the wettability to an adherend and therefore is preferred. On the other hand, use of 25 mass % or less makes it possible to secure the coating workability and therefore is preferred.
The solvent (8) is preferably selected from high boiling solvents having a boiling point falling in a range of 150 to 230xc2x0 C., preferably 160 to 200xc2x0 C.
It shall not specifically be restricted, and specific examples of the preferred solvent (8) include, for example, ketone solvents such as cyclohexanone, ether solvents and acetate solvents.
More specific examples of the ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and diethylene glycol diphenyl ether.
The acetate solvents are represented, for example, by ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diacetate, diethylene glycol monomethyl acetate, diethylene glycol monoethyl acetate, diethylene monobutyl ether acetate and diethylene glycol diacetate.
The particularly preferred solvent (8) is at least one selected from ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol diacetate.
The gap-forming controller (9) means a substance which can control optionally and accurately a gap width of a liquid crystal display element to a prescribed width of, for example, 3 to 7 xcexcm. It doesn""t matter whether the substance is organic or inorganic.
The gap-forming controller (9) is suitably added, if necessary, preferably in a proportion of 0.1 to 5 mass %, more preferably 0.5 to 2.5 mass based on the composition for a liquid crystal display cell sealant of the present invention.
The gap-forming controller (9) includes, for example, vertically and horizontally symmetric inorganic particles or thermosetting polymer particles such as spherical or rugby ball-like particles and cylindrical fibers which are not deformed, dissolved or swollen by the epoxy resin (1) or the solvent (8) that is added if necessary.
Examples of the inorganic particles in the gap-forming controller include spherical silica particles, spherical alumina particles, glass short fibers, metal short fibers and metal powders.
The organic gap-forming controller includes thermosetting polystyrene spherical particles, other phenol resin base thermosetting particles and benzoguanamine resin base thermosetting particles.
The inorganic particles are particularly preferred since they can control the gap accuracy at a high accuracy.
A leveling agent, a pigment, a dye, a plasticizer and a defoaming agent can further be used, if necessary.
Production Process for Liquid Crystal Sealant Composition:
The liquid crystal sealant composition of the present invention can be prepared by suitably adding and mixing the epoxy resin (1) having 1.2 or more epoxy groups on an average in a molecule, the rubber-like polymer fine particle (2) having a softening point of 0xc2x0 C. or lower and a primary particle diameter of 5 xcexcm or less, the inorganic filler (3), the potential curing agent for epoxy resin (4), the high softening point-polymer fine particle (5) having a softening point of 50xc2x0 C. or higher and a primary particle diameter of 2 xcexcm, and if necessary, the silane coupling agent (6), the curing accelerator (7), the solvent (8), the gap-forming controller (9) and other additives, and the method shall not specifically be restricted.
They may be mixed by means of a known kneading machine such as a double arm stirrer, a roll mixer, a twin screw extruder and a ball mill, and the composition is subjected to vacuum degassing treatment, finally charged into a glass bottle or a plastic vessel and tightly sealed, stored and transported.
Physical Properties of the Liquid Crystal Sealant Composition:
The viscosity of the liquid crystal sealant composition before curing shall not specifically be restricted, and the viscosity at 25xc2x0 C. determined by an E type viscometer falls preferably in a range of 1 to 1000 Paxc2x7s, more preferably 5 to 500 Paxc2x7s and most preferably 10 to 200 Paxc2x7s. The liquid crystal sealant composition of the present invention is controlled in advance to a viscosity of this range by heating and aging and then produced.
The thixotropic index represented by, for example, a ratio of a viscosity value at 0.5 rpm to a viscosity value at 5 rpm (viscosity value at 0.5 rpm/viscosity value at 5 rpm), which are obtained by using the same rotor number of an E type viscometer, tough not specifically restricted, falls preferably in a range of 1 to 10.
Production Process for Liquid Crystal Display Cell:
A production process for the liquid crystal display cell of the present invention, comprising:
printing or dispenser-coating the liquid crystal sealant composition of the present invention on a bonding-sealing part of a glass-made or plastic-made substrate for a liquid crystal cell and precuring it at 80 to 100xc2x0 C.,
adjusting the position in a pair with a substrate which is not subjected to the treatment described above, and
then subjecting the paired substrates to hot press treatment at 100 to 200xc2x0 C. to bond and fix the above paired substrates in a homogeneous thickness falling in a prescribed range of, for example, 3 to 7 xcexcm.
In this case, precuring is required in advance in order to completely cure the liquid crystal sealant composition containing a solvent, bond and seal it. The precuring conditions shall not specifically be restricted. A heating and drying temperature at which the solvent contained can preferably be removed by at least 95 mass %, and which is not higher than a thermally active temperature of the potential curing agent for epoxy resin contained is preferably selected.
General precuring conditions are a temperature falling in a range of 80 to 100xc2x0 C. and a drying time falling in a range of 5 to 60 minutes. The drying time is preferably shortened as the temperature is elevated. The solvent can be removed even in precuring at a temperature exceeding 100xc2x0 C., but an accuracy in the gap width tends to be reduced by progress in the curing reaction, and therefore attentions have to be paid.
The substrate used for the liquid crystal cell includes, for example, a glass substrate and a plastic substrate. It is A matter of course in the preceding substrates that used is a so-called liquid crystal cell-constituting glass substrate or plastic substrate in which provided on needed parts are a transparent electrode represented by indium oxide, an alignment film represented by polyimide and in addition thereto, an inorganic ion-shielding film and the like.
A method of coating the liquid crystal sealant composition on a substrate shall not specifically be restricted and includes, for example, a screen printing coating method and a dispenser coating method. After coating, predrying is carried out, if necessary, and then bonding is carried out by superimposing and hot press bonding. In this case, hot curing conditions shall not specifically be restricted and are 100 to 200xc2x0 C. for 24 to 0.5 hours.
In carrying out a hot press step by means of a single layer hot press, a condition under which a temporary adhesive property can be secured shall not specifically be restricted. Preferably, after bonded at 110 to 200xc2x0 C. for 2 to 10 minutes, the pressure is reduced to take out the substrate, and subsequently it is completely cured in a heated oven controlled to the same temperature, whereby bonding is carried out through two-stage or plural heating steps and aging steps.
In this case, the single layer hot press means a hot press machine having a specification to carry out bonding set by set. Known are a vacuum single layer hot press which is a single layer hot press apparatus capable of heating under vacuum and a normal single layer hot press of a type in which hot press bonding is forcibly carried out via a hot plate under atmospheric pressure. It may be either single layer hot press system.
Also, it causes no any problems to carry out the hot press bonding described above by a multistage hot press separately from the single layer hot press.
Liquid Crystal Display Element:
The liquid crystal display element of the present invention is a liquid crystal display element obtained by:
printing or dispenser-coating the liquid crystal sealant composition of the present invention on a bonding-sealing part of a glass-made or plastic-made substrate for a liquid crystal cell and precuring it at 70 to 120xc2x0 C.,
then adjusting the position in a pair with a substrate which is not subjected to the treatment described above,
subjecting the paired substrates to hot press treatment at 100 to 200xc2x0 C. to bond and fix in a homogeneous thickness falling in a prescribed range of, for example, 3 to 7 xcexcm to obtain a cell, and
then charging a liquid crystal material into the above cell and sealing the injection port with a two-liquid type liquid crystal sealant composition.
The above two-liquid type liquid crystal sealant composition shall not specifically be restricted, and any one can be used as long as the effects of the present invention are not damaged. Given as examples thereof are, for example, a two-liquid type liquid crystal sealant composition comprising an epoxy resin and a polyamide curing agent, a two-liquid type liquid crystal sealant composition comprising an epoxy resin and a polythiol curing agent and a two-liquid type liquid crystal sealant composition comprising an epoxy resin and a polyamine curing agent.
The liquid crystal material shall not be restricted, and nematic liquid crystal and ferroelectric liquid crystal are suited.
Preferred examples of the liquid crystal display element used in the present invention include, for example, a TN type (twisted nematic) liquid crystal element and an STN type (super twisted nematic) liquid crystal element which are proposed by M. Schadt and W. Helfrich, a ferroelectric type liquid crystal element proposed by N. A. Clark and S. T. Lagerwall and a liquid display crystal element provided on each pixel with a thin film transistor.